Photographic element with 2-equivalent magenta dye-forming coupler and filter dye

ABSTRACT

A photographic element is described having 
     a photographic support; 
     a green sensitive silver halide emulsion layer on the photographic support and having a magenta dye-forming coupler, and 
     a filter layer on the photographic support and associated with the green sensitive layer, wherein the magenta dye-forming coupler is a 2-equivalent magenta dye-forming coupler, and the filter layer includes a filter dye molecule having the formula: 
     
         D═CH--M                                                (I) 
    
     wherein D is a group which, with the remainder of the molecule, forms a dye having an absorption maximum in the blue or green region of the visible spectrum, and 
     M is a five-membered or six-membered unsaturated heterocyclic ring, which may be fused with another five-membered or six-membered ring system, and which is unsubstituted or substituted with a lower alkyl group having from 1 to 10 carbon atoms, or an electron withdrawing group.

FIELD OF THE INVENTION

This invention relates to color photographic elements, particularlythose with one or more of the light sensitive layers protected againstexposure to light in the blue and/or green region of the spectrum by ayellow and/or a magenta filter dye layer(s).

BACKGROUND OF THE INVENTION

Color silver halide photographic materials generally contain layer unitssensitive to each of the primary regions of the visible spectrum, i.e.,the blue, green, and red regions, and coupler compounds. Such couplercompounds have the function of producing dyes to make up the imagesrecorded in such materials. Usually, a yellow dye-forming coupler isassociated with a blue sensitive silver halide emulsion layer, a magentadye-forming coupler is associated with a green sensitive silver halideemulsion layer, and a cyan dye-forming coupler is associated with a redsensitive silver halide emulsion layer.

Silver halide employed in these materials has inherent sensitivity inthe blue region of the visible spectrum. Increased sensitivity to bluelight, along with sensitivity to green light or red light, is impartedthrough the use of various sensitizing dyes adsorbed on the silverhalide grains. Sensitized silver halide, however, retains its intrinsicsensitivity to blue light, and, therefore, the red sensitive and greensensitive layers of color photographic elements are sensitive toradiation in the blue region of the spectrum as well as to radiation inthe region of the spectrum intended to be recorded, i.e., green or redradiation, respectively.

If, prior to processing, blue light reaches a layer containing silverhalide sensitized to a region of the spectrum other than blue, suchexposed silver halide grains would be rendered developable, resulting ina false rendition of the image information recorded by the photographicelement. It is common, therefore, to incorporate in the photographicelement a material that filters blue light. This blue absorbing materialcan be located anywhere in the element where the filtering of blue lightis desirable. In a photographic element with layers sensitized to eachof the primary colors, it is common to have the blue sensitive layerclosest to the exposure source and to impose a blue-absorbing, oryellow, filter layer between the blue sensitive layer and green and redsensitive layers.

Similarly, if the red layer sensitization is broad enough to respond tounwanted green light exposure, a false rendition of color is observed.In such instances, the use of a magenta filter dye residing below thegreen sensitive silver halide emulsion layer, but above the redsensitive layers, is advantageous. The green light is absorbed, and thusdoes not expose the red sensitive layers.

The material most commonly used as a blue-absorbing material inphotographic elements is yellow colloidal silver, known in the art asCarey Lea silver. Carey Lea silver, however, exhibits unwantedabsorption in the green region of the spectrum. Silver can also causeunwanted photographic fog. Filter dyes can provide the beneficial lightabsorption properties without the undesirable effects of Carey Leasilver. Examples of materials useful as filter dyes are those describedin U.S. Pat. Nos. 4,420,555 to Krueger et al. and 4,923,788 toShuttleworth et al.

There are many known classes of compounds that are useful as couplers inphotographic materials. 5-Pyrazolone compounds and pyrazoloazole (e.g.,pyrazolotriazole) compounds are well-known as magenta dye-formingcouplers. Such couplers are described in, for example, James, The Theoryof the Photographic Process, MacMillan, 1977. One type of magentadye-forming coupler is the 4-equivalent type. With 4-equivalentcouplers, a hydrogen atom is cleaved from the coupler compound at thecoupling position when the compound couples with the oxidized colordeveloper. Four moles of silver halide must be reduced in order to formone mole of dye from a 4-equivalent coupler.

A second type of magenta dye-forming coupler known in the art is the2-equivalent type. As described below, such couplers require thereduction of two moles of silver halide to form one mole of dye.

When a 4-equivalent magenta dye-forming coupler is incorporated in agreen sensitive layer adjacent to a filter layer having a certain knowntype of filter dye, an unacceptable increase in light-induced yellowingor "printout" of the post-processing image occurs. Therefore, a problemto be solved by this invention is a reduction in the printout increasewhich occurs when certain filter dyes are used in conjunction with4-equivalent magenta dye-forming couplers. Elements of this type havebeen described in U.S. Pat. No. 4,923,788 to Shuttleworth et al.

Although the problem of an increase in printout is significant for bothof the two major types of photographic elements, color negative andcolor reversal elements, it is a more serious problem with colorreversal materials.

In color negative materials, the element is exposed to light andprocessed with a color developer that imagewise forms a silver image anda dye image. The silver image is formed due to the color developer'sreduction of exposed silver halide to form silver and oxidized colordeveloper. The dye image is formed by the reaction of oxidized colordeveloper with dye-forming coupler. The silver image is bleached andsolubilized for removal, leaving only a negative color dye image. Thisimage is then used to expose another color negative material to form apositive color dye image.

In contrast, in reversal materials, the element is generally exposed andprocessed with a black-and-white developer to form a negative silverimage in each layer. The remaining undeveloped silver halide thus formsa positive imagewise pattern. The undeveloped silver halide is thenfogged and processed in a color developer to form a dye image along withthe silver. All the silver is then bleached and solubilized for removal,leaving only the positive color dye image.

In color negative photography, the photographic element that was exposedto the image is thus used to print the finished product on a secondphotographic material. The effect of an unwanted increase in printoutmay be lessened through the use of various filters in conjunction withthe printing equipment. No such masking opportunity exists with colorreversal materials, because the element originally exposed to the imagebecomes the finished product upon processing. Any increase in printoutis, therefore, more likely to be apparent in the final image with colorreversal materials.

SUMMARY OF THE INVENTION

The present invention relates to photographic elements incorporatingcertain filter dye compounds in filter layers adjacent to greensensitive layers having a specific type of magenta dye-forming coupler.It has been found that the printout increase which occurs when certainfilter dyes are used in conjunction with 4-equivalent magentadye-forming couplers can be reduced by replacing the 4-equivalentcouplers with 2-equivalent magenta dye-forming couplers.

Specifically, a photographic element in accordance with the inventioncomprises a photographic support, a green sensitive silver halideemulsion layer on the photographic support and having a magentadye-forming coupler, and a filter layer having a filter dye, associatedwith the green sensitive layer, wherein the magenta dye-forming coupleris a 2-equivalent magenta dye-forming coupler and the filter dyemolecule has the formula:

    D═CH--M                                                (I)

wherein D is a group which, with the remainder of the molecule, forms adye having an absorption maximum in the blue or green region of thevisible spectrum, and

M is a five-membered or six-membered unsaturated heterocyclic ring,which may be fused with another five-membered or six-membered ringsystem, and which is unsubstituted or substituted with a lower alkylgroup having from 1 to 10 carbon atoms, or an electron withdrawinggroup.

2-Equivalent magenta dye-forming couplers differ from 4-equivalentmagenta dye-forming couplers in the type of group cleaved from theremainder of the coupler at the coupling position. In 4-equivalentcouplers, as described above, a hydrogen atom is cleaved at the couplingposition during development, whereas, the group cleaved from a2-equivalent coupler at the coupling position during coupling with anoxidized color developer is a coupling-off group, such as a halogen orother displaceable group. 2-Equivalent couplers require the reduction oftwo moles of silver halide to silver to form one mole of dye.

In contrast to results obtained with photographic elements incorporatingthese filter dyes in filter layers associated with green sensitivelayers having 4-equivalent magenta dye-forming couplers, elements inaccordance with the invention exhibit no deleterious increase inprintout following processing.

DETAILED DESCRIPTION OF THE INVENTION

As described above, a photographic element in accordance with theinvention comprises:

a photographic support;

a green sensitive silver halide emulsion layer on the photographicsupport and having a magenta dye-forming coupler; and

a filter layer on the photographic support associated with said greensensitive layer, wherein the magenta dye-forming coupler is a2-equivalent magenta dye-forming coupler, and the filter layer comprisesa filter dye molecule having the formula:

    D═CH--M                                                (I)

wherein D is a group which, with the remainder of the filter dye, formsa dye having an absorption maximum in the blue or green region of thevisible spectrum, and

M is a five-membered or six-membered unsaturated heterocyclic ring,which may be fused with another five-membered or six-membered ringsystem, and which is unsubstituted or substituted with a lower alkylgroup having from 1 to 10 carbon atoms, or an electron withdrawinggroup.

By "associated with," it is meant that the green sensitive silver halidelayer is either adjacent to the filter layer or otherwise sufficientlyclose to the filter layer so that the layers and/or their constituentsoperatively interact. While not wishing to be bound by theory, in somecases this operative interaction may involve the reaction of the magentadye-forming coupler and the filter dye in their entireties and/orfragments thereof.

By "electron withdrawing group" it is meant a group having a Hammett's σpara value exceeding 0.3. Hammett's σ constants are described, forexample, in Hansch et al. "Aromatic" Substituent Constants forStructure-Activity Correlations vol. 16, no. 11, 1207-1217 (1973).Examples of suitable electron withdrawing groups are a cyano group, anitro group, substituted or unsubstituted carbamoyl groups having from 1to 30 carbon atoms, such as methylcarbamoyl, ethylcarbamoyl,4-methoxy-phenylcarbamoyl, N-methyl-N-octadecylcarbamoyl,3-(2,4-di-pentylphenoxy)propylcarbamoyl, pyrrolidinocarbonyl,hexadecylcarbamoyl and di-n-octyl-carbamoyl groups, substituted orunsubstituted sulfamoyl groups having from 1 to 30 carbon atoms, such asmethylsulfamoyl, diethylsulfamoyl,3-(2,4-di-t-pentyl-phenoxy)propylcarbamoyl, phenylsulfamoyl,pyrrolidinosulfonyl and morpholinosulfonyl groups, substituted orunsubstituted alkoxycarbonyl groups having from 1 to 30 carbon atoms,such as methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl,2-methoxyethoxycarbonyl, and hexadecyloxycarbonyl groups, substituted orunsubstituted sulfonyl groups having from 1 to 30 carbon atoms, such asmethanesulfonyl, 4-methyl-phenylsulfonyl and dodecylsulfonyl groups,substituted or unsubstituted acyl groups having from 1 to 30 carbonatoms, such as acetyl, hexanoyl, benzoyl and 4-chloro-benzoyl groups, atrifluoromethyl group, a carboxyl group, and substituted orunsubstituted heterocyclic residues having from 1 to 30 carbon atoms,such as benzoxazole-2-yl and 5,5-dimethyl-2-oxazoline-2-yl groups, asdescribed in U.S. Pat. No. 4,740,453.

When M is a six-membered heterocyclic ring, the ring preferably containsat least one nitrogen atom. Examples of useful heterocyclic ringsinclude furan, thiophene, pyridine, pyrrole, and imidazole. These ringsmay be substituted with any of a number of known substituents including,but not limited to sulfo, sulfato, sulfonamido (e.g.,butanesulfonamido), amido, amino, carboxyl, halogen, alkoxy, hydroxy,acyl, phenyl, alkyl, and the like. The substituents can be locatedessentially anywhere on the ring or rings comprising M.

The 2-equivalent magenta dye-forming couplers useful in the practice ofthe invention can be members of any of the classes of couplers that arewell-known in the art, as described, for example, in theabove-referenced James, The Theory of the Photographic Process. Theseinclude both 5-pyrazolone couplers and pyrazoloazole couplers such aspyrazolotriazole couplers. In a preferred embodiment, the 2-equivalentmagenta dye-forming couplers are ballasted couplers, which havesufficient bulk to be incorporated in particular layers of thephotographic element.

2-Equivalent 5-pyrazolone couplers as a class are well-known to oneskilled in the art. The couplers may be polymeric or non-polymeric, asdescribed, for example, in commonly assigned and co-pending U.S.application Ser. No. 696,313 of Bowne, filed Apr. 30, 1991.Non-polymeric 2-equivalent 5-pyrazolone couplers which are useful in thepresent invention include the following: ##STR1## wherein R³ is acarbonamido group, an arylamino group, a ureido group, a sulfonamidogroup, an alkylamino group, or a heterocyclic amino group,

R⁴ is a substituted or unsubstituted alkyl or aryl group, and

X is a group capable of being released by a coupling reaction with anoxidized aromatic primary amine developing agent (hereinafter a"coupling-off" group).

Such coupling-off groups are known in the art and may include a groupcontaining an aliphatic group, an aromatic group, a heterocyclic group,an aliphatic, aromatic, or heterocyclic sulfonyl group, or an aliphatic,aromatic, or heterocyclic carbonyl group that is bonded to the couplingactive carbon via an oxygen atom, a nitrogen atom, a sulfur atom, or acarbon atom, a halogen atom, an aromatic azo group, and the like. Thealiphatic, aromatic, or heterocyclic group contained in suchcoupling-off groups may have one or more substituents, as describedbelow.

Examples of coupling-off groups include a halogen atom (e.g., fluorine,chlorine, bromine), an alkoxy group (e.g., ethoxy, dodecycloxy,carboxypropyloxy), and aryloxy group (e.g., 4-chlorophenoxy group, a4-methoxyphenoxy group), an acyloxy group (e.g., an acetoxy group, atetradecanoloxy group), an aliphatic or aromatic sulfonyloxy group(e.g., a methanesulfonyloxy group, a toluenesulfonyloxy group), anacylamino group (e.g., a dichloroacetylamino group, atrifluoroacetylamino group), an aliphatic or aromatic sulfonamido group(e.g., a methanesulfonamido group, a p-toluenesulfonamido group), analkyloxycarbonyloxy group (e.g., an ethoxycarbonyloxy group), anaryloxycarbonyloxy group (e.g., a benzyloxycarbonyloxy group, aphenoxycarbonyloxy group), an aliphatic, aromatic or hetercyclic thiogroup (e.g., an ethylthio group, a phenylthio group), a carbamoylaminogroup (e.g., an N-methylcarbamoylamino group, an N-phenylcarbamoylaminogroup), a 5-membered or 6-membered nitrogen-containing heterocyclicgroup (e.g., an imidazolyl group, a pyrazolyl group), an imido group(e.g., a succinimido group, a hydantoinyl group), an aromatic azo group(e.g., a phenylazo group), and the like.

The aliphatic, aromatic, or heterocyclic groups encompassed by X and thegroups covered by R³ and R⁴ may be substituted by a substituent such as,for example a halogen atom (e.g., a fluorine atom, a chlorine atom, abromine atom, etc.), an alkyl group (e.g., a methyl group, a t-octylgroup, a dodecyl group, a trifluoromethyl group, etc.), an alkenyl group(e.g., an allyl group, an octadecenyl group, etc.), an aryl group (e.g.,a phenyl group, a p-tolyl group, a naphthyl group, etc.), an alkoxygroup (e.g., a methoxy group, a benzyloxy group, a methoxyethoxy groupetc.), an aryloxy group (e.g., a phenoxy group, a2,4-di-tert-amylphenoxy group, a 3-tert-butyl-4-hydroxyphenoxy group,etc.), an acyl group (e.g., an acetyl group, a benzoyl group, etc.), asulfonyl group (e.g., a methanesulfonyl group, a toluenesulfonyl group,etc.), a carboxy group, a sulfo group, a cyano group, a hydroxy group,an amino group (e.g., a primary amino group, a dimethylamino group,etc.), a carbonamido group (e.g., an acetamido group, atrifluoroacetamido group, a tetradecanamido group, a benzamido group,etc.), a sulfonamido group (e.g., a methanesulfonamido group, ahexadecanesulfonamido group, a p-toluenesulfonamido group, etc.), anacyloxy group (e.g., an acetoxy group, etc.), a sulfonyloxy group (e.g.,a methanesulfonyloxy group, etc.), an alkoxycarbonyl group (e.g., adodecyloxycarbonyl group, etc.), an aryloxycarbonyl group (e.g.,phenoxycarbonyl group, etc.), a carbamoyl group (e.g., adimethylcarbamoyl group a sulfamoyl group (e.g., a methylsulfamoylgroup, a hexadecylsulfamoyl group, etc.), an imido group (e.g., asuccinimido group, a phthalimido group, an octadecenylsuccinimido group,etc.), a heterocyclic group (e.g., a 2-pyridyl group, a 2-furyl group, a2-thienyl group, etc.), an alkylthio group (e.g., a methylthio group,etc.), and an arylthio group (e.g., a phenylthio group, etc.).

Another example of a coupler having a releasable group through a carbonatom for X is a so-called bis type coupler obtained by condensing a4-equivalent coupler with an aldehyde or a ketone.

Any one of R³, R⁴ and X may be a divalent or a more polyvalent group toform an oligomer such as a dimer, etc., or may connect a polymeric mainchain and a coupler skeleton to form a polymeric coupler, as shown belowin formulas (III), (IV), and (V). ##STR2## In these formulas, R6represents an alkyl group, a substituted alkyl group (e.g., a haloalkylgroup such as fluoroalkyl, or cyanoalkyl and benzylalkyl groups), or asubstituted or unsubstituted aryl group. Examples of the substituentinclude an alkyl group (e.g., a methyl group and an ethyl group), analkoxyl group (e.g., a methoxy group and an ethoxy group), an aryloxygroup (e.g., a phenyloxy group), an alkoxycarbonyl group (e.g., amethoxycarbonyl group), an acylamino group (e.g., an acetylamino group),a carbamoyl group, an alkylcarbamoyl group (e.g., a methylcarbomoylgroup and an ethylcarbamoyl group), a dialkylcarbamoyl group (e.g., adimethylcarbamoyl group), an arylcarbamoyl group (e.g., aphenylcarbamoyl group), an alkylsulfonyl group (e.g., a methylsulfonylgroup), an alkylsulfonamido group (e.g., a methanesulfonamido group), anarylsulfonamido group (e.g., a phenylsulfonamido group), a sulfamoylgroup, an alkylsulfamoyl group (e.g., an ethylsulfamoyl group), adialkylsulfamoyl group (e.g., a dimethylsulfamoyl group), an alkylthiogroup (e.g., a methylthio group), an arylthio group (e.g., a phenylthiogroup), a cyano group, a nitro group, and a halogen atom (e.g.,fluorine, chlorine and bromine); when the aryl group is substituted withtwo or more substituents, they may be the same or different.

When R⁶ is an aryl group, preferred examples of the substituent are ahalogen atom, an alkyl group, an alkoxyl group, an alkoxycarbonyl group,and a cyano group. A particularly preferred substituent is a halogenatom.

R⁵ is a substituted or unsubstituted arylamino group (e.g., an anilinogroup), a carbonamido group (e.g., an alkylcarbonamido group, aphenylcarbonamido group, an alkoxycarbonamido group and aphenyloxycarbonamido group), a ureido group (e.g., an alkylureido groupand a phenylureido group), a sulfonamido group, and alkylamino group, aheterocyclic amino group, and preferably is a carbonamido group.

X is a coupling-off group as defined above. Particularly preferredexamples of the releasable group are nitrogen atom-containing releasablegroups forming a heterocyclic ring such as an imidazolyl group and apyrazolyl group, and sulfur atom-containing releasable groups such as analkylthio group and an arylthio group.

X¹ represents a divalent group, derived from X, having bonding sites tothe pyrazolone ring and to --(Y)_(q) -- in formulas (VI) and (VII),below.

In formulas (III), (IV) and (V), * indicates a site where the structureis linked to --(Y)_(q) -- in the formulas (VI) and (VII): ##STR3## Informulas (VI) and (VII), R⁷ is a hydrogen atom, a lower alkyl grouphaving from 1 to 4 carbon atoms, or a chlorine atom,

A is --CONH--, --COO--, --O--, or a phenylene group,

B is a substituted or unsubstituted straight or branched alkylene group,aralkylene group, or phenylene group,

Y is --CONR'--, --NR'CONR'--, --NR'COO--, --NR'CO--, --OCONR'--,--NR'--, --COO--, --OCO--, --CO--, --O--, --SO₂ --, --NR'SO₂ -- or --SO₂NR'--, wherein R' is a hydrogen atom or a substituted or unsubstitutedaliphatic group or aryl group, and when two or more R's are present inone molecule, R's may be same or different,

q is 0 or 1,

p is 0 when q is 0, or 1 when q is 1, and

Q represents the 2-equivalent magenta coupler structure of formulas(III), (IV), and (V).

The polymer couplers useful in the present invention may be homopolymersof monomer couplers represented by formula (VI), or a copolymer of twoor more of monomer couplers represented by formula (VI), or a copolymerof a monomer coupler of formula (VI) and one or more non-color-formingethylenic monomers which does not couple with an oxidized product of anaromatic primary amine developing agent. Even in this case, as themonomer coupler of formula (VI), a copolymer comprising two or more of amonomer couplers represented by formula (VI) together with one or morenon-color-forming ethylenical monomers may be used.

The ethylenical monomer not forming color on coupling with an oxidizedproduct of an aromatic primary amine developing agent includes acrylicacid, α-chloroacrylic acid, α-alkylacrylic acid (e.g., methacrylicacid), and their ester or amide derivatives (e.g., acrylamide,methacrylamide, n-butylacrylamide, tertbutylacrylamide,diacetoneacrylamide, methylenebisacrylamide, methyl methacrylate, ethylacrylate, n-propyl acrylate, n-butyl acrylate, tert-butyl acrylate,iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, laurylacrylate, methyl methacrylate, ethyl methacrylate, n-butylmethacrylate,and β-hydroxyl methacrylate), vinyl esters (e.g., vinyl acetate, vinylpropionate and vinyl laurate), acrylonitrile, methacrylonitrile,aromatic vinyl compounds (e.g., styrene and its derivatives, such asvinyltoluene, divinylbenzene, vinylacetophenone and sulfonstyrene),itaconic acid, citraconic acid, crotonic acid, vinylidene chloride,vinyl alkyl ethers (e.g., vinyl ethyl ether), maleic acid esters,N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine.

Particularly preferred examples are acrylic acid esters, methacrylicacid esters, and maleic acid esters. The above non-color formingethylenically unsaturated monomers can be used as mixtures comprisingtwo or more thereof. Typical examples are a combination of methylacrylate and butyl acrylate, a combination of butyl methacrylate andmethacrylic acid, and a combination of methyl acrylate and diacetoneacrylamide.

As is well known in the polymer coupler field, the type of theethylenically unsaturated monomer to be copolymerized with the monomercoupler of the general formula (V) can be chosen appropriately so as toexert favorable influences on the physical and/or chemical properties ofthe resulting copolymer, such as solubility, compatibility with a binder(e.g., gelatin) of a photographic colloid composition, flexibility, andheat stability.

The magenta polymer coupler as used herein can be conveniently handledin the form of a latex during the preparation of light-sensitivematerial. This latex can be prepared by two methods. In one method, anolephilic polymer coupler, as prepared by polymerization of the abovemonomer coupler, is dissolved in an organic solvent and then dispersedor emulsified in an aqueous gelatin solution. In the other method, adirect emulsion polymerization is carried out. The former method isdescribed in U.S. Pat. No. 3,451,820, and the latter method is describedin U.S. Pat. Nos. 4,080,211 and 3,370,952.

As a polymerization initiator and a polymerization solvent for use inthe synthesis of the magenta polymer coupler of the present invention,compounds as described in Japanese patent applications (OPI) 81/5543,82/94752, (i.e., U.S. Pat. No. 4,367,282) 82/176038 (i.e., U.S. Pat. No.4,388,404), 82/204038 (i.e., U.S. Pat. No. 4,416,978) 83/28745 (i.e.,U.S. Pat. No. 4,409,320), 83/10738, 83/42044, 83/145944 (i.e., U.S. Pat.No. 4,436,808), 83/224352 and 84/42543 (i.e., German Patent No.2,127,984B) can be used.

The polymerization temperature is determined from the molecular weightof the polymer formed, the type of polymerization initiation, etc. Thepolymerization temperature can be between 0° and 100° C., usually, 30°to 100° C.

The proportion of the color forming portion of the monomer of formula(V) in the copolymer coupler is usually from 5 to 80 wt %. In view ofcolor reproductivity, color forming properties and stability, theproportion is preferably from 20 to 70 wt %. In this case, the molecularweight equivalent (i.e., the number of grams of the polymer containing 1mol of the monomer coupler) is preferably (but not necessarily) fromabout 250 to 4,000.

Where groups above are described as substituted or unsubstituted, unlessotherwise indicated, substituents for the groups can include, forexample, a halogen atom, an alkyl group, an aryl group, a heterocyclicgroup, a cyano group, an alkoxy group, and aryloxy group, a heterocyclicoxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, asulfonyloxy group, and acylamino group, an anilino group, a ureidogroup, an imido group, a sulfonylamino group, an arylthio group, acarbamoylamino group, an alkylthio group, a heterocyclic thio group, analkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamidogroup, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonylgroup, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonylgroup, an alkenyl group, a carboxyl group, a sulfo group, a hydroxylgroup, an amino group, and a carbonamido group, etc. R⁵ preferablyrepresents an arylamino group, a carbonamido group, a sulfonamido groupor a ureido group and R⁶ preferably is a substituted aryl group.

Examples of polymeric 2-equivalent 5-pyrazolone couplers include:##STR4##

Other 2-equivalent 5-pyrazolone couplers which are useful in the presentinvention are described in U.S. Pat. Nos. 4,791,051, 4,863,841, and4,367,282, which are hereby incorporated herein by reference.

Another useful class of magenta couplers are pyrazoloazole couplers, asdescribed, for example, in commonly assigned and co-pending U.S.application Ser. No. 568,398, filed Aug. 16, 1990. Pyrazoloazolecouplers useful in the practice of the invention include those accordingto the formula: ##STR5## wherein R⁸ is a hydrogen atom or a substitutedor unsubstituted alkyl, aryl, alkoxy or aryloxy group.

X is as defined above for formula (II), and

J represents the non-metallic atoms necessary to complete a heterocyclicring.

A more specific expression of compounds according to formula (VIII) isformula (IX): ##STR6## wherein R⁸ is a hydrogen atom or a substituted orunsubstituted alkyl, aryl, alkoxy or aryloxy group.

X is as defined above for formula (II),

J¹, J², and J³ each represents a substituted or unsubstituted methinegroup, ═N--, or --NH--, wherein:

one of either the J¹ --J² bond or the J² --J³ bond is a double bond withthe other being a single bond,

when the J² --J³ bond is a carbon-carbon double bond, it may form partof an aromatic ring, and

when any one of R⁸, X, and a substituted methine group represented byJ¹, J², or J³ is a divalent or polyvalent group, it may form a dimer ora polymer.

Examples of 2-equivalent magenta dye-forming couplers useful in thepractice of the invention are presented below. ##STR7##

The filter dyes useful in the practice of the invention are thoseaccording to formula (I) above. Such filter dyes are well-known in thephotographic art. Some are shown and described in the above-referencedU.S. Pat. No. 4,923,788 to Shuttleworth, et al., which is herebyincorporated by reference.

More specifically, filter dyes useful in the present invention includethose having the formula (X): ##STR8## wherein D is as defined above forformula (I), T is --O--, --S--, or --NR² --, wherein R² is a bridgingbonding valence, a hydrogen atom, or a lower alkyl group having from 1to 4 carbon atoms,

R¹ is a hydrogen atom, a lower alkyl group having from 1 to 10 carbonatoms, or an electron withdrawing group, and

Z represents the atoms necessary to complete a five-membered orsix-membered unsaturated heterocyclic ring containing T and additionallyup to one nitrogen atom, the remainder of the ring atoms being carbonatoms.

By "bridging bonding valence" is meant electrons available for forming adouble bond.

Preferred filter dyes according to formulas (I) and (X) are morespecifically represented by the formula (XI): ##STR9## wherein D and Tare as described above for formula (X) and Z¹, Z², and Z³ eachindependently represents --CR¹⁰ -- or --N--, wherein at least two of Z¹,Z², and Z³ are --CR¹⁰ -- and each R¹⁰ is independently a hydrogen atom,a lower alkyl group having from 1 to 10 carbon atoms or, an electronwithdrawing group.

In one embodiment of the invention, filter dyes useful in the presentinvention include those having the formula (XII): ##STR10## wherein R isa substituted or unsubstituted alkyl group or aryl group, X² is anelectron withdrawing group,

L¹ and L² are each independently a substituted or unsubstituted methinegroup, and

n is 0 or a positive integer from 1 to 6.

Preferred alkyl groups for R have from 1 to 20 carbon atoms and includestraight chain alkyls such as methyl, ethyl, propyl, butyl, pentyl,decyl, dodecyl, etc., branched alkyl groups such as isopropyl, isobutyl,t-butyl, and the like. These alkyl groups may be substituted with any ofa number of known substituents, such as sulfo, sulfato, sulfonamido,amido, amino, carboxyl, halogen, alkoxy, hydroxy, phenyl, and the like.The substituents may be located essentially anywhere on the alkyl group.The possible substituents are not limited to those exemplified, and oneskilled in the art could easily choose from a number of substitutedalkyl groups that would provide useful compounds according to formula(X).

Preferred aryl groups for R have 6 to 10 carbon atoms (e.g., phenyl,naphthyl), which may be substituted. Useful substituents for the arylgroup include any of a number of known substituents for aryl groups,such as sulfo, sulfato, sulfonamido (e.g., butanesulfonamido), amido,amino, carboxyl, halogen, alkoxy, hydroxy, acyl, phenyl, alkyl, and thelike. Additionally, the aryl group may have substituents that form fusedring systems with it, such as naphthyl. The substituents can be locatedessentially anywhere on the ring. The possible substituents are notlimited to those exemplified, and one skilled in the art could easilychoose from a number of substituted aryl groups that would provideuseful compounds according to formula (X).

X² represents an electron withdrawing group, as described above forformula (I). Electron withdrawing groups in organic compounds arewell-known in the art, such as described in J. Marsh, Advanced OrganicChemistry, 3rd. Ed., the disclosure of which is hereby incorporatedherein by reference in its entirety. Useful electron withdrawing groupsinclude, for example, cyano, substituted or unsubstituted carboxylate(preferably having 2 to 7 carbon atoms, e.g., COR¹¹ where R¹¹ is asubstituted or unsubstituted alkyl or aralkyl), and COR⁹ where R⁹ is aprimary or secondary amino group, and aryl groups (either unsubstitutedor substituted with an electron withdrawing group, e.g., phenyl,p-nitrophenyl, p-cyanophenyl, 3,4-dichlorophenyl). The possiblesubstituents for the various X² and R¹¹ groups will be known to thoseskilled in the art and include those described herein for R.

In another embodiment of the invention, filter dyes useful in thepresent invention include those having the formula (XIII): ##STR11##wherein X² is as defined above for formula (XII), R¹⁴ is a substitutedor unsubstituted aryl or heterocyclic group, and

R¹⁵ is an oxygen atom, or ##STR12## wherein R¹² and R¹³, which may bethe same or different, are each independently substituted orunsubstituted alkyl or aryl groups, carbonyl groups, cyano groups,nitrogen- or oxygen-containing heterocyclic groups, primary or secondaryamino groups, or oxygen atoms,

and wherein R¹² and R¹³ may bond to form a ring, as indicated by thedashed line connecting R¹² and R¹³ in formula (XIV).

Useful substituents for R¹², R¹³ and R¹⁴ include those described abovefor R.

Examples of useful filter dyes according to formula (I) are shown below:##STR13##

The dyes of formula (I) can be prepared by well known chemical synthetictechniques, as described, for example, in U.S. Pat. No. 4,923,788 and inHamer, The Cyanine Dyes and Related Compounds, Interscience Publishers1964.

The present invention is particularly useful for color reversal systems,which unlike color negative systems, do not offer the option ofcompensating for unwanted printout during the printing process. Inreversal processes, the photographic element is free of coloredcouplers. The latent image is developed first in a black-and-whitedeveloper, thus using up the exposed silver halide. Then, the residualsilver halide is activated either by exposure or chemically, therebybecoming developable. In the presence of color developing agents, theactivated silver halide in a blue sensitive layer is developed to yieldprimarily a yellow dye. In a green sensitive layer, it yields primarilya magenta dye, and, in a red sensitive layer, it produces primarily acyan dye. All of the developed silver is then removed.

In contrast, colored couplers are incorporated in the layers of a colornegative photographic element. The presence of these couplers masksundesirable absorptions of the negative image for printing onto a secondphotographic material. The color negative can be printed onto a similarmaterial to obtain, after processing, a positive image.

In a preferred embodiment of the invention, the photographic element isa color reversal photographic element, such as those processable inKodak E-6® processing (e.g., Kodak Ektachrome® products, FujiFujichrome® products). E-6® processing is described in British Journalof Photography Annual, 1977 pp. 194-197.

The photographic support of the element of the present invention can beany of a number of well-known supports for photographic elements. Theseinclude polymeric films such as cellulose esters (e.g., cellulosetriacetate and diacetate) and polyesters of dibasic aromatic carboxylicacids with divalent alcohols (e.g., poly(ethylene terephthalate)),paper, and polymer-coated paper. Such supports are described in furtherdetail in Research Disclosure, December, 1989, Item 308119 [hereinafterreferred to as Research Disclosure I], Section XVII.

The silver halide emulsion used in the practice of the invention cancontain, for example, silver bromide, silver chloride, silver iodide,silver chlorobromide, silver chloroiodide, silver bromoiodide, ormixture thereof. The emulsions can include coarse, medium, or finesilver halide grains bounded by 100, 111, or 110 crystal planes. Silverhalide emulsions and their preparation are further described in ResearchDisclosure I, Section I. Also useful are tubular grain silver halideemulsions, as described in Research Disclosure, January, 1983, Item22534 and U.S. Pat. No. 4,425,426.

The 2-equivalent magenta dye-forming couplers (or mixtures of suchcouplers) and the filter dye of formula (I) (or mixtures of such filterdyes), when used according to the present invention, can be incorporatedin layers of photographic materials by techniques well-known in the art.One common technique involves the use of high-boiling water-immiscibleorganic solvents and/or surfactants. Useful organic solvents includetricresyl phosphates, di-n-butyl phthalate, and others described inResearch Disclosure I, Section XI. Mixtures of solvents and surfactantsmay also be used.

The filter dyes, when used according to the present invention, can beincorporated in the layers of the photographic materials by techniqueswell-known in the art. A preferred method involves the use of these dyesas solid particle dispersions as described in U.S. Pat. No. 4,940,654 toDiehl et al., which is hereby incorporated by reference.

The silver halide described above can be sensitized to a particularwavelength range of radiation, such as the red, blue, or green portionsof the visible spectrum, or other wavelength ranges, such asultraviolet, infrared, and the like. In a preferred embodiment, thesilver halide emulsion associated with the 2-equivalent magentadye-forming coupler is spectrally sensitized to green light so as tocomplement the magenta color of the dye formed by the coupler duringprocessing. Chemical sensitization of silver halide can be accomplishedwith chemical sensitizers such as gold compounds, iridium compounds, orother group VIII metal compounds. Spectral sensitization is accomplishedwith spectral sensitizing dyes such as cyanine dyes, merocyanine dyes,styryls, or other known spectral sensitizers. Additional information onsensitization of silver halide is described in Research Disclosure I,Sections I-IV.

The filter dye of formula (I) and the 2-equivalent magenta dye-formingcoupler may be located in any of a number of associated layers of aphotographic element, depending on the specific requirements of theelement and the dye, and on the manner in which the element is to beexposed. Either the filter dye-containing filter layer on the greensensitive layer containing the 2-equivalent magenta dye-forming couplerof a given pair of adjacent layers may be closer to the support than theother.

The photographic element of the present invention may be a color elementor monochromatic. Multicolor photographic elements according to theinvention generally comprise a blue sensitive silver halide layer havinga yellow color-forming coupler associated therewith, a green sensitivelayer having a magenta color-forming coupler associated therewith, and ared sensitive silver halide layer having a cyan color-forming couplerassociated therewith. Color photographic elements and color-formingcouplers are well-known in the art and are further described in ResearchDisclosure I, Section VII.

The element of the invention can also include any of a number of otherwell-known additives and layers, as described in Research Disclosure I.These include, for example, optical brighteners, antifoggants, oxidizeddeveloper scavengers, development accelerators, image stabilizers,light-absorbing materials such as filter layers or intergrain absorbers,light-scattering materials, gelatin hardeners, coating aids and varioussurfactants, overcoat layers, interlayers and barrier layers, antistaticlayers, plasticizers and lubricants, matting agents, developmentinhibitor-releasing couplers, bleach accelerator-releasing couplers, andother additives and layers known in the art.

The photographic elements of the invention, when exposed, are processedto yield an image. Processsing can be by any type of known photographicprocessing, as described in Research Disclosure I, Sections XIX-XXIV. Anegative image can be developed by color development with a chromogenicdeveloping agent followed by bleaching and fixing. A positive image canbe developed by sequentially developing with a non-chromogenicdeveloper, uniformly fogging the element, and developing with achromogenic developer.

Bleaching and fixing can be performed with any of the materials known tobe used for that purpose. Bleach baths generally comprise an aqueoussolution of an oxidizing agent such as water soluble salts and complexesof iron (III) (e.g., potassium salts of ferricethylenediaminetetraacetic acid), water-soluble persulfates (e.g.,potassium, sodium, or ammonium persulfate), water-soluble dichromates(e.g., potassium, sodium, and lithium dichromate), and the like. Fixingbaths generally comprise an aqueous solution of compounds that formsoluble salts with silver ions, such as sodium thiosulfate, ammoniumthiosulfate, potassium thiocyanate, sodium thiocyanate, thiourea, andthe like.

The invention is further illustrated by the following Examples:

EXAMPLE 1

A cellulose triacetate film support provided with a subbing layer wascoated with each layer having the composition set forth below to preparea multilayer color photographic light-sensitive material, which wasdesignated sample 101.

In the composition of the layers, the coating amounts are shown as g/m²except for sensitizing dyes, which are shown as the molar amount permole of silver halide present in the same layer.

    ______________________________________                                        First Layer: Antihalation Layer                                               Black Coloidal Silver   0.43 (as silver)                                      Gelatin                 2.44                                                  Second Layer: Intermediate Layer                                              Gelatin                 1.22                                                  Third Layer: Slow Red Sensitive Layer                                         Silver Iodobromide Emulsion                                                                           0.36 (as silver)                                      Red Sensitizing Dyes    1.42 × 10.sup.-3                                Cyan Coupler C-1        0.54                                                  Solvent-2               0.27                                                  Gelatin                 0.86                                                  Fourth Layer: Fast Red Sensitive Layer                                        Silver Iodobromide Emulsion                                                                           0.48 (as silver)                                      Red Sensitizing Dyes    1.05 × 10.sup.-3                                Cyan Coupler C-1        0.97                                                  Solvent-2               0.49                                                  Gelatin                 1.51                                                  Fifth Layer: Intermediate Layer                                               Competitor-1            0.16                                                  Dye-1                   0.06                                                  Gelatin                 0.61                                                  Sixth Layer: Intermediate Layer                                               Gelatin                 0.61                                                  Seventh Layer: Slow Green Sensitive Layer                                     Silver Iodobromide Emulsion                                                                           0.32 (as silver)                                      Sensitizing Dye-1       1.50 × 10.sup.-3                                Sensitizing Dye-2       0.5 × 10.sup.-3                                 Coupler M-2             0.35                                                  Coupler M-1             0.15                                                  Solvent-1               0.25                                                  Gelatin                 0.86                                                  Eighth Layer: Fast Green Sensitive Layer                                      Silver Iodobromide Emulsion                                                                           0.43 (as silver)                                      Sensitizing Dye-1       0.75 × 10.sup.-3                                Sensitizing Dye-2       0.25 × 10.sup.-3                                Coupler M-2             0.60                                                  Coupler M-1             0.26                                                  Solvent-1               0.43                                                  Gelatin                 1.51                                                  Ninth Layer: Yellow Filter Layer                                              Dye-2                   0.27                                                  Gelatin                 0.61                                                  Tenth Layer: Intermediate Layer                                               Competitor-1            0.11                                                  Gelatin                 0.61                                                  Eleventh Layer: Slow Blue Sensitive Layer                                     Silver Iodobromide Emulsion                                                                           0.22                                                  Blue Sensitizing Dye    1.08 × 10.sup.-3                                Coupler Y-1             0.70                                                  Solvent-2               0.23                                                  Gelatin                 1.08                                                  Twelfth Layer: Fast Blue Sensitive Layer                                      Silver Iodobromide Emulsion                                                                           0.54                                                  Blue Sensitizing Dye    1.60 × 10.sup.-3                                Coupler Y-1             1.56                                                  Solvent-2               0.52                                                  Gelatin                 2.37                                                  Thirteenth Layer: First Protective Layer                                      Competitor-1            0.06                                                  Gelatin                 1.40                                                  Ultraviolet Absorbing Dyes                                                                            0.51                                                  Fourteenth Layer: Second Protective Layer                                     Fine Grain Silver Bromide                                                                             0.12 (as silver)                                      (0.07μ equivalent spherical diameter)                                      Matte                   0.02                                                  (3.3μ spherical diameter)                                                  Bis(vinyl sulfonyl methane)                                                                           0.26                                                  Gelatin                 0.97                                                  ______________________________________                                    

Samples 102 to 104 were prepared in the same manner as described abovefor Sample 101 except that the 4-equivalent magenta dye-forming couplersM-1 and M-2 in the Seventh and Eighth Layers in Sample 101 were replacedwith the 2-equivalent magenta dye-forming couplers A, B, and C in thoselayers in Samples 102, 103, and 104, respectively. No Solvent-1 was usedin either the Seventh or Eighth layers of Sample 104.

Each of the samples thus prepared was cut into a 35 mm width strip. Thesamples were stepwise exposed and were processed using standard KodakE-6® processing solutions and methods. The Status A blue Dmin densitieswere measured using a densitometer. The samples were then allowed torest for 24 hrs. on a lighted table top illuminator. After exposure, theStatus A blue Dmin was again measured. The measured densities for theprocessed samples both before and after light exposure are listed inTable I.

                  TABLE I                                                         ______________________________________                                                                            Status A                                                                      B Dmin                                                                        after  Δ Sta-                                        g/m.sup.2                                                                            g/m.sup.2                                                                          Initial                                                                              24 hrs tus A                                      Magenta  7th    8th  Status A                                                                             on light                                                                             B                                  Sample No.                                                                            Coupler  layer  layer                                                                              B Dmin table  Dmin                               ______________________________________                                        101 (Com-                                                                             M-2      0.35   0.60 0.14   0.23   +0.09                              parison)                                                                              M-1      0.15   0.26                                                  102     A        0.51   0.86 0.12   0.11   -0.01                              (invention)                                                                   103     B        0.32   0.56 0.12   0.11   -0.01                              (invention)                                                                   104     C        0.68   1.15 0.14   0.14   0.00                               (invention)                                                                   ______________________________________                                    

From the results shown in Table I, a significant amount of undesirableblue density in the Dmin region of the coating is generated for thesample containing the 4-equivalent magenta couplers (Sample 101) in thefilm with yellow filter dye-2. This yellow stain is avoided when thesample contains a 2-equivalent magenta coupler (Samples 102-104) usedwith yellow filter Dye-2.

EXAMPLE 2

On a cellulose triacetate film support provided with a subbing layer wascoated each layer having the composition set forth below to prepare amultilayer color photographic light-sensitive material, which isdesignated Sample 201.

In the composition of the layers, the coating amounts are shown as g/m²except for sensitizing dyes, which are shown as the molar amount permole of silver halide present in the same layer.

    ______________________________________                                        First Layer: Antihalation Layer                                               Black Coloidal Silver   0.43                                                  Gelatin                 2.44                                                  Second Layer: Intermediate Layer                                              Fine Grain Silver Bromide                                                                             0.05 (as silver)                                      (0.07μ equivalent spherical diameter)                                      Competitor-1            0.05                                                  Gelatin                 1.22                                                  Third Layer: Slow Red Sensitive Layer                                         Silver Iodobromide Emulsion                                                                           0.84                                                  Red Sensitizing Dyes    0.45 × 10.sup.-3                                Cyan Coupler C-1        0.27                                                  Solvent-2               0.14                                                  Gelatin                 2.44                                                  Fourth Layer: Fast Red Sensitive Layer                                        Silver Iodobromide Emulsion                                                                           0.97 (as silver)                                      Red Sensitizing Dyes    0.33 × 10.sup.-3                                Cyan Coupler C-1        0.98                                                  Solvent-2               0.49                                                  Gelatin                 2.26                                                  Fifth Layer: Intermediate Layer                                               Competitor-1            0.11                                                  Dye-1                   0.05                                                  Gelatin                 0.75                                                  Sixth Layer: Intermediate Layer                                               Silver Iodobromide Emulsion                                                                           0.54 (as silver)                                      Sensitizing Dye-1       0.46 × 10.sup.-3                                Sensitizing Dye-2       0.21 × 10.sup.-3                                Coupler M-2             0.13                                                  Coupler M-1             0.05                                                  Solvent-1               0.09                                                  Gelatin                 0.97                                                  Seventh Layer: Fast Green Sensitive Layer                                     Silver Iodobromide Emulsion                                                                           0.75 (as silver)                                      Sensitizing Dye-1       1.02 × 10.sup.-3                                Sensitizing Dye-2       0.38 × 10.sup.-3                                Coupler M-2             0.67                                                  Coupler M-1             0.29                                                  Solvent-1               0.48                                                  Gelatin                 1.72                                                  Eighth Layer: Yellow Filter Layer                                             Dye-2                   0.22                                                  Gelatin                 0.72                                                  Ninth Layer: Intermediate Layer                                               Competitor-1            0.11                                                  Gelatin                 0.61                                                  Tenth Layer: Slow Blue Sensitive Layer                                        Silver Iodobromide Emulsion                                                                           1.34                                                  Blue Sensitizing Dye    0.39 × 10.sup.-3                                Coupler Y-1             1.42                                                  Solvent-2               0.71                                                  Gelatin                 2.23                                                  Bis(vinyl sulfonyl methane)                                                                           0.27                                                  Eleventh Layer: Fast Blue Sensitive Layer                                     Silver Iodobromide Emulsion                                                                           0.37                                                  Blue Sensitizing Dye    0.39 × 10.sup.-3                                Coupler Y-1             0.38                                                  Solvent-2               0.19                                                  Gelatin                 0.61                                                  Twelfth Layer: First Protective Layer                                         UV Absorbing Dyes       0.51                                                  Gelatin                 1.40                                                  Thirteenth Layer: Second Protective Layer                                     Fine Grain Silver Bromide                                                                             0.12 (as silver)                                      (0.07μ equivalent spherical diameter)                                      Matte                   0.02                                                  (3.3μ spherical diameter)                                                  Gelatin                 0.98                                                  ______________________________________                                    

Samples 202 and 203 were prepared in the same manner as sample 201, butsample 202 contained no yellow Filter Dye-2 in the Eighth Layer, whilesample 203 contained 0.09 g/m² Carey Lea Silver (CLS) in place of Dye-2in the Eighth Layer.

Each of the samples thus prepared was cut into a 35 mm strip. Thesamples were stepwise exposed and were processed using standard KodakE-6® processing solutions and methods. The status A blue Dmin densitieswere measured using a densitometer. The samples were then placed on alighted table top illuminator for 28 days, followed by reading of StatusA blue Dmin densities by densitometry. The measured densities before andafter treatment are listed in Table II.

                  TABLE II                                                        ______________________________________                                                                       Status A                                             Yellow            Initial                                                                              B Dmin after                                                                           Δ                               Sample                                                                              Filter   g/m.sup.2                                                                              Status A                                                                             24 hours on                                                                            Status A                              No.   Material in Layer B Dmin Light Table                                                                            B Dmin                                ______________________________________                                        201   Dye-2    0.22     0.16   0.24     0.08                                  202   None     0.00     0.13   0.13     0.00                                  203   CLS      0.09     0.14   0.14     0.00                                  ______________________________________                                    

From the results in Table II, the undesirable yellow printout stain isgenerated an the sample containing both the 4-equivalent magentacouplers M-1 and M-2 and yellow filter Dye-2. The presence of yellowfilter dye is necessary, in combination with the 4-equivalent magentacoupler to produce the problem. The benefits of yellow filter dye canonly be realized without stain generation when used in combination witha 2-equivalent magenta coupler.

The components employed for the preparation of the light-sensitivematerials not already identified above are shown below. ##STR14##

Although the invention has been described in considerable detail withparticular reference to certain preferred embodiments thereof,variations and modifications can be effected within the spirit and scopeof the invention.

What is claimed is:
 1. A photographic element, comprising:a photographicsupport; a green sensitive silver halide emulsion layer on saidphotographic support and having a magenta dye-forming coupler; and afilter layer on said photographic support and associated with said greensensitive layer, wherein said magenta dye-forming coupler is a2-equivalent magenta dye-forming coupler, and said filter layercomprises a filter dye molecule having the formula:

    D═CH--M                                                (I)

wherein D is a group which, with the remainder of the molecule, forms adye having an absorption maximum in the blue or green region of thevisible spectrum, M is a five-membered or six-membered unsaturatedheterocyclic ring, which may be fused with another five-membered orsix-membered ring system, and which is unsubstituted or substituted witha lower alkyl group having from 1 to 10 carbon atoms, or an electronwithdrawing group.
 2. A photographic element according to claim 1,wherein said 2-equivalent magenta dye-forming coupler has the formula:##STR15## wherein R³ is a carbonamido group, an arylamino group, aureido group, a sulfonamido group, an alkylamino group, or aheterocyclic amino group,R⁴ is a substituted or unsubstituted alkyl oraryl group, and X is a group capable of being released by a couplingreaction with an oxidized aromatic primary amine developing agent.
 3. Aphotographic element according to claim 1, wherein said magentadye-forming coupler has the formula: ##STR16## wherein R⁵ is asubstituted or unsubstituted arylamino group, carbonamido group, ureidogroup, sulfonamido group, alkylamino group, or heterocyclic aminogroup,R⁶ is a substituted or unsubstituted alkyl group or aryl group, Xis a group capable of being released by a coupling reaction with anoxidized aromatic primary amino developing agent, X¹ represents adivalent group derived from X having bonding sites to the pyrazolonering and to --(Y)_(q) -- in formulas (VI) and (VII) below, * representsa site for linkage to --(Y)_(q) -- in the formulas (VI) and (VII):##STR17## wherein R⁷ is a hydrogen atom, a lower alkyl group having from1 to 4 carbon atoms, or a chlorine atom, A is --CONH--, --COO--, --O--,or a phenylene group, B is a substituted or unsubstituted straight orbranched chain alkylene group, aralkylene group, or a phenylene group, Yis --CONR'--, --NR'CONR'--, --NR'COO--, --NR'CO--, OCONR'--, --NR'--,--COO--, --OCO--, --CO--, --O--, --SO₂ --, --NR'SO₂ -- or --SO₂ NR'--,wherein R' is a hydrogen atom or a substituted or unsubstitutedaliphatic group or aryl group, and when two or more R's are present inone molecule, the R's may be the same or different, q is 0 or 1, p is 0when q is 0, or 1 when q is 1, and Q represents the structure offormulas (III), (IV), and (V).
 4. A photographic element according toclaim 3, wherein R⁵ is an anilino group.
 5. A photographic elementaccording to claim 2, wherein R³ is an anilino group.
 6. A photographicelement according to claim 1, wherein said 2-equivalent magentadye-forming coupler has the formula: ##STR18## wherein R⁸ is a hydrogenatom or a substituted or unsubstituted alkyl, aryl, alkoxy or aryloxygroup.X is a group capable of being released by a coupling reaction withan oxidized aromatic primary amine developing agent, and J representsthe non-metallic atoms necessary to complete a heterocyclic ring.
 7. Aphotographic element according to claim 6, wherein said 2-equivalentmagenta dye-forming coupler has the formula: ##STR19## wherein J¹, J²,and J³ each represents a substituted or unsubstituted methine group,═N--, or --NH--, whereone of either the J¹ --J² bond or the J² --J³ bondis a double bond with the other being a single bond, when the J² --J³bond is a carbon--carbon double bond, it may form part of an aromaticring, and when any one of R⁸, X, and a substituted methine grouprepresented by J¹, J², or J³ is a divalent or polyvalent group, said2-equivalent magenta dye-forming coupler may form a dimer or a polymer.8. A photographic element according to claim 1, wherein M is selectedfrom the group consisting of furan, thiophene, pyridine, pyrrole, andimidazole.
 9. A photographic element according to claim 1, wherein saidfilter dye has the formula: ##STR20## wherein T is --O--, --S--, or--NR² --, wherein R² is a bridging bonding valence, a hydrogen atom, ora lower alkyl group having from 1 to 4 carbon atoms,R¹ is a hydrogenatom, a lower alkyl group having from 1 to 10 carbon atoms, or anelectron withdrawing group, and Z represents the atoms necessary tocomplete a five-membered or six-membered unsaturated heterocyclic ringcontaining T and additionally up to 1 nitrogen atom, the remainder ofthe ring atoms being carbon atoms.
 10. A photographic element accordingto claim 9, wherein said filter dye has the formula: ##STR21## whereinZ¹, Z², and Z³ each independently represents --CR¹⁰ -- or --N--, whereinat least two of Z¹, Z², and Z³ are --CR¹⁰ -- and each R¹⁰ isindependently a hydrogen atom, a lower alkyl group having 1 to 10 carbonatoms, or an electron withdrawing group.
 11. A photographic elementaccording to claim 9, wherein said filter dye has the formula: ##STR22##wherein R is a substituted or unsubstituted alkyl group or aryl group,X² is an electron withdrawing group,L¹ and L² are each independently asubstituted or unsubstituted methine group, and n is 0 or a positiveinteger from 1 to
 6. 12. A photographic element according to claim 11,wherein X² is selected from the group consisting of cyano, substitutedor unsubstituted carboxylate, substituted or unsubstituted aryl, and--COR⁹ --, wherein R⁹ is a primary or secondary amino group.
 13. Aphotographic element according to claim 11, wherein n is
 0. 14. Aphotographic element according to claim 11, wherein X² is cyano.
 15. Aphotographic element according to claim 9, wherein said filter dye hasthe formula ##STR23## wherein X² is an electron withdrawing group, R¹⁴is a substituted or unsubstituted aryl or heterocyclic group, andR¹⁵ isan oxygen atom, or ##STR24## wherein R¹² and R¹³, which may be the sameor different, are each independently substituted or unsubstituted alkylor aryl groups, carbonyl groups, cyano grups, nitrogen- oroxygen-containing heterocyclic groups, primary or secondary aminogroups, or oxygen atoms, and wherein R¹² and R¹³ may bond to form aring, as indicated by the dashed line connecting R¹² and R¹³ in formula(XIV).
 16. A photographic element according to claims 1, 2, 3, 9, 10,11, or 15, wherein the element is a color reversal photographic element.17. A photographic element according to claims 1, 2, 3, 9, 10, 11 or 15,wherein the element is a color negative photographic element.
 18. Aphotographic element according to claim 11, wherein the filter dye isselected from the group consisting of: ##STR25##
 19. A photographicelement according to claim 15, wherein the filter dye is selected fromthe group consisting of ##STR26##
 20. A photographic element accordingto claim 1, wherein the magenta dye-forming coupler is selected from thegroup consisting of: ##STR27##
 21. A photographic element according toclaim 1, wherein said filter layer is closer to said support than saidgreen sensitive layer.
 22. A photographic element according to claim 1,wherein said green sensitive layer is closer to said support than saidfilter layer.
 23. A photographic element free of colored couplers,comprising:a photographic support; a green sensitive silver halideemulsion layer on said photographic support and having a magentadye-forming coupler; and a filter layer on said photographic support andassociated with said green sensitive layer, wherein said magentadye-forming coupler is a 2-equivalent magneta dye-forming coupler, andsaid filter layer comprises a filter dye molecule having the formula:

    D═CH--M                                                (I)

wherein D is a group which, with the remainder of the molecule, forms adye having an absorption maximum in the blue or green region of thevisible spectrum, and M is a five-membered or six-membered unsaturatedheterocyclic ring, which may be fused with another five-membered orsix-membered ring system, and which is unsubstituted or substituted witha lower alkyl group having from 1 to 10 carbon atoms, or an electronwithdrawing group.
 24. A photographic element according to claim 23,wherein said magenta dye-forming coupler has the formula: ##STR28##wherein R⁵ is a substituted or unsubstituted arylamino group,carbonamido group, uneido group, sulfonamido group, alkylamino group, orheterocyclic amino group,R⁶ is a substituted or unsubstituted alkylgroup or aryl group, X is a group capable of being released by acoupling reaction with an oxidized aromatic primary amino developingagent, X¹ represents a divalent group derived from X having bondingsites to the pyrazolone ring and to --(Y)_(q) -- in formulas (VI) and(VII) below, *represents a site for linkage to --(Y)_(q) -- in theformulas (VI) and (VII): ##STR29## wherein R⁷ is a hydrogen atom, alower alkyl group having from 1 to 4 carbon atoms, or a chlorine atom, Ais --CONH--, --COO--, --O--, or a phenylene group, B is a substituted orunsubstituted straight or branched chain alkylene group, aralkylenegroup, or a phenylene group, Y is --CONR'--, --NR'CONR'--, --NR'COO--,--NR'CO--, OCONR'--, --NR'--, --COO--, --OCO--, --CO--, --O--, --SO₂ --,--NR'SO₂ -- or --SO₂ NR'--, wherein R' is a hydrogen atom or asubstituted or unsubstituted aliphatic group or aryl group, and when twoor more R's are present in one molecule, R's may be the same ordifferent, q is 0 or 1, p is 0 when q is 0, or 1 when q is 1, and Qrepresents the structure of formulas (III), (IV), and (V), and whereinsaid filter dye has the formula: ##STR30##